CN114656504A - Ruthenium carbene catalyst and preparation method and application thereof - Google Patents
Ruthenium carbene catalyst and preparation method and application thereof Download PDFInfo
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- CN114656504A CN114656504A CN202011524065.8A CN202011524065A CN114656504A CN 114656504 A CN114656504 A CN 114656504A CN 202011524065 A CN202011524065 A CN 202011524065A CN 114656504 A CN114656504 A CN 114656504A
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- ruthenium carbene
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- isopropoxybenzene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- -1 tri (4-isopropoxybenzene) phosphine Chemical compound 0.000 claims abstract description 25
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical group 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- MPAOOLLBWUEXOM-UHFFFAOYSA-N 1-bromo-4-propan-2-yloxybenzene Chemical compound CC(C)OC1=CC=C(Br)C=C1 MPAOOLLBWUEXOM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011986 second-generation catalyst Substances 0.000 claims description 2
- 239000012258 stirred mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000005865 alkene metathesis reaction Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011984 grubbs catalyst Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a ruthenium carbene catalyst, a preparation method thereof and application thereof in catalyzing ring-opening metathesis reaction. The carbene structure ruthenium catalyst has the structural formula shown as follows:
Description
Technical Field
The invention relates to a ruthenium carbene structural compound and the technical field of synthesis thereof, in particular to a ruthenium carbene catalyst and a preparation method thereof, and application of the ruthenium carbene catalyst in catalyzing ring-opening metathesis reaction.
Background
Olefin metathesis is the process by which two broken olefin carbon-carbon double bonds recombine into new carbon-carbon double bonds. It can be widely used in the synthesis of natural products and in material science.
The most influential factor on olefin metathesis reactions is the catalyst. For many years, the search for efficient, specific catalysts has been the focus of research in olefin metathesis. In view of the contributions Schrock, Grubbs, Chauvin three have made on olefin metathesis catalysts, the 2005 nobel prize of chemistry was obtained jointly.
Among the olefin metathesis catalyst systems, Grubbs' catalyst (Grubbs catalyst), a ruthenium carbene structured compound, is most widely used and is increasingly widely used in the pharmaceutical and material industries due to its stability to oxygen and protic solvents. And because of the good tolerance to polar groups containing protons, the method plays an important role in the synthesis of various molecules needing to use olefin metathesis reaction to construct a new macrocyclic structure.
Disclosure of Invention
The invention aims to provide a ruthenium carbene catalyst, a preparation method thereof and application thereof in catalyzing ring-opening metathesis double decomposition reaction. The ruthenium catalyst with the carbene structure is prepared by reacting ruthenium carbene catalyst with pyridine to obtain ruthenium carbene catalyst containing pyridine, reacting 1-bromine-4-isopropoxybenzene with magnesium and phosphorus trichloride to obtain tri (4-isopropoxybenzene) phosphine, and reacting the ruthenium carbene catalyst containing pyridine with the tri (4-isopropoxybenzene) phosphine.
The technical scheme of the invention is as follows:
the first purpose of the invention is to provide a ruthenium carbene catalyst, which has the following structural formula:
a second object of the present invention is to provide a method for preparing the ruthenium carbene catalyst, comprising:
(1) dissolving and mixing the Grubbs second-generation catalyst (II) and a pyridine compound in an organic solvent, stirring for reaction, and performing post-treatment to obtain a green ruthenium carbene catalyst (III) containing pyridine;
wherein the GrubbsII catalyst has a structure shown in a formula (II):
the structure of the ruthenium carbene catalyst containing pyridine is shown as the formula (III):
wherein R is H, CH3
(2) 1-bromine-4-isopropoxybenzene and crushed magnesium chips are placed in an organic solvent, after reflux reaction is carried out for 2 hours at room temperature, phosphorus trichloride is added into reaction liquid, heating and reflux are carried out for 2 hours, and then the reaction liquid is extracted, thus obtaining ligand tri (4-isopropoxybenzene) phosphine (IV);
wherein the ligand tri (4-isopropoxy benzene) phosphine has a structure shown in a formula (IV):
(3) dissolving the ruthenium carbene catalyst (III) containing pyridine prepared in the step (1) by using an organic solvent, adding the ligand tris (4-isopropoxybenzene) phosphine (IV) prepared in the step (2), stirring for reaction until the color of the solution is brown, and performing post-treatment to obtain the ruthenium carbene structural compound shown in the formula (I).
Further, the mass ratio of the Grubbs secondary catalyst (II) to the pyridine compound in the step (1) is 1: 1-5; the preferred mass ratio is 1: 1-2.
Further, the stirring reaction temperature in the step (1) is 10-40 ℃, and the reaction time is 10min-1 h; the reaction temperature is preferably 5-25 ℃ and the reaction time is 10-20 min.
Further, the organic solvent in the step (1) is selected from one or a mixture of more of dichloromethane, trichloromethane, tetrachloromethane, tetrahydrofuran, trichlorobenzene, toluene or benzene; preferred organic solvents are toluene or benzene.
Further, the post-processing in the step (1) specifically comprises the following operations: transferring the stirred mixture into a low-temperature solvent through a sleeve, sequentially precipitating, filtering, washing and drying under vacuum to obtain a ruthenium carbene catalyst (III) containing pyridine; wherein the solvent is alkane, naphthenic hydrocarbon or aromatic hydrocarbon compound with the carbon atom number less than 20; preferably the solvent is pentane or hexane.
Further, the mol ratio of the 1-bromo-4-isopropoxybenzene to the magnesium to the phosphorus trichloride in the step (2) is 1-10:1-10: 1; the preferred molar ratio is 3-4:3-4: 1.
Further, the organic solvent in the step (2) is one or a mixture of more of anhydrous ether, tetrahydrofuran, dioxane and dimethyl sulfoxide; the preferred solvent is anhydrous diethyl ether.
Further, in the step (2), 1-bromo-4-isopropoxybenzene and crushed magnesium chips are placed in an organic solvent, heated for reflux reaction for 2 hours, then slowly cooled to room temperature, phosphorus trichloride is slowly dripped into the reaction solution at the ambient temperature of-100-0 ℃, then heating and refluxing are continuously carried out for 2 hours, and the ligand tri (4-isopropoxybenzene) phosphine (IV) is obtained by extracting the reaction solution.
Further, the extracting agent used in the extraction in the step (2) is alkane, naphthenic hydrocarbon or aromatic hydrocarbon compounds with carbon number less than 20; the preferred extractant is anhydrous diethyl ether.
Further, the molar ratio of the ruthenium carbene catalyst (III) containing pyridine to the ligand tri (4-isopropoxy benzene) phosphine (IV) in the step (3) is 1: 1-5; the preferred molar ratio is 1:1 to 1.5.
Further, the organic solvent in the step (3) is selected from one or a mixture of more of dichloromethane, trichloromethane, tetrachloromethane, tetrahydrofuran, trichlorobenzene, toluene or benzene; preferably the solvent is toluene or benzene.
Further, the post-processing in the step (3) specifically comprises the following operations: removing the solvent from the stirred solution in vacuum, washing the obtained residue with the solvent, and drying in vacuum to obtain the ruthenium carbene structural compound shown in the formula (I); wherein the solvent is alkane, naphthenic hydrocarbon or aromatic hydrocarbon compound with the carbon atom number less than 20; preferably the solvent is pentane or hexane.
Further, the stirring reaction temperature in the step (3) is 5-30 ℃, and the reaction time is 5min-1 h; the reaction temperature is preferably 15-25 ℃ and the reaction time is 5-20 min.
Further, the preparation method is carried out under the protection of nitrogen in all steps.
The third purpose of the invention is to provide the application of the ruthenium carbene catalyst in catalyzing reactions such as olefin ring-opening metathesis reaction, ring-closing metathesis reaction or cross metathesis and the like.
Further, the olefin ring-opening metathesis in the application method specifically comprises the following steps: dissolving the ruthenium carbene catalyst in an organic solvent to obtain a mixed solution A, dissolving dicyclopentadiene, a modifier and an antioxidant in the organic solvent to obtain a mixed solution B, fully and uniformly mixing the mixed solution A and the mixed solution B, immediately injecting the mixed solution A and the mixed solution B into a mold, carrying out ring-opening metathesis reaction on olefin at 40-80 ℃, curing and forming, and carrying out post-treatment at 120-150 ℃.
Further, the organic solvent in the application method is one or a mixture of more of dichloromethane, toluene, ethyl acetate or tetrahydrofuran.
Further, the mass ratio of the dicyclopentadiene to the ruthenium carbene catalyst is 5000-50000: 1.
Further, the temperature of the olefin ring-opening metathesis reaction is 50-70 ℃, and the reaction time is 5-10 minutes.
The reaction mechanism of the present invention is as follows:
wherein, R is H or CH 3.
Compared with the prior art, the invention has the beneficial effects that:
the novel carbene structure ruthenium catalyst synthesized by the invention has the tris (4-alkoxy phenyl) phosphine ligand, and in the catalytic polymerization process, compared with the traditional ruthenium metal carbene structure catalyst, the tris (4-alkoxy phenyl) phosphine ligand is easy to fall off to form a catalyst active center, so that the initiation rate of the catalyst is improved, and the reaction speed is accelerated.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
The starting materials used in the following examples are all commercially available.
Example 1
The No. 1 ruthenium carbene catalyst and the synthesis method thereof:
under nitrogen, a second generation Grubbs catalyst (from ann, girald chemical co., ltd) (4.0g) was dissolved in toluene (10mL) and pyridine (30mL) was added. The reaction was stirred at room temperature for 10 minutes during which time a color change from red to bright green was observed. The reaction mixture was transferred through cannula to 100mL of cold (-10 ℃) pentane and a green solid precipitated. The precipitate was filtered, washed with 4X 50mL pentane and dried under vacuum to give a green powder of pyridine-containing intermediate.
Under the protection of nitrogen, a constant-pressure dropping funnel and a reflux condenser tube are quickly arranged on a dried 250m L three-necked bottle, 4.8g of crushed magnesium chips are added into the three-necked bottle, 50mL of anhydrous ether is added for covering, 3.8mL of 1-bromine-4-isopropoxybenzene is added dropwise, one particle of iodine is added, and heating and refluxing are carried out. When the color of iodine fades to become grey turbid liquid, 36.2g of 1-bromo-4-isopropoxybenzene and 100mL of anhydrous ether are prepared into a mixed solution, the mixed solution is placed in a constant-pressure dropping funnel, a small amount of the mixed solution is slowly dropped into a reaction bottle, heat is released for reflux, and after the dropping is finished, the mixed solution is heated for reflux for 2 hours. And (2) placing the reaction bottle at-78 ℃, slowly dropwise adding a mixed solution of 7.3g of phosphorus trichloride and 20mL of anhydrous ether, heating and refluxing for 2 hours after dropwise adding, slowly cooling to room temperature, hydrolyzing by using an ammonium chloride aqueous solution, separating an organic phase by using a flow-dividing funnel, extracting a water layer by using ether, combining the organic phase and an extract, drying by using anhydrous magnesium sulfate, distilling off the ether under reduced pressure, distilling under reduced pressure by using an oil pump, collecting a fraction of 160-class organic solvent, and obtaining the phosphorus ligand at 200 ℃.
The intermediate (150mg) and phosphine ligand (90mg) were combined in benzene (10mL) under nitrogen and stirred at room temperature for 10 min. The solvent was removed in vacuo and the resulting brown residue was washed with 4X 20mL of pentane and dried in vacuo. The compound was obtained as a brown powder.
The product has the following spectrogram analysis data:
the molecular formula is as follows: c55H65N2O3PCl2Ru
m/z：1004.67(100％)
Elemental Analysis：C:66.09；H:6.39；P:3.02
HNMR(400MHz)：
δ＝7.52-7.44(5H,m)；4.15-4.76(39H,m)；2.23-2.75(21H,m)。
Example 2
The No. 2 ruthenium carbene catalyst and the synthesis method thereof:
under nitrogen, the dibasic Grubbs catalyst (4.0g) was dissolved in toluene (10mL) and 2-methylpyridine (32mL) was added. The reaction was stirred at room temperature for 15 minutes during which time a color change from red to bright green was observed. The reaction mixture was transferred through a cannula into 100mL of cold (-10 ℃) pentane and a green solid precipitated. The precipitate was filtered, washed with 4X 50mL pentane and dried under vacuum to give a green powder of pyridine-containing intermediate.
Under the protection of nitrogen, a constant-pressure dropping funnel and a reflux condenser tube are quickly arranged on a dried 250m L three-necked bottle, 5.0g of crushed magnesium chips are added into the three-necked bottle, 50mL of anhydrous ether is added for covering, 3.8mL of 1-bromine-4-isopropoxybenzene is added dropwise, and one piece of iodine is added for heating and refluxing. When the color of iodine fades to become grey turbid liquid, 36.2g of 1-bromo-4-isopropoxybenzene and 100mL of anhydrous ether are prepared into a mixed solution, the mixed solution is placed in a constant-pressure dropping funnel, a small amount of the mixed solution is slowly dropped into a reaction bottle, heat is released for reflux, and after the dropping is finished, the mixed solution is heated and refluxed for 2 hours. And (2) placing the reaction bottle at-78 ℃, slowly dropwise adding a mixed solution of 8.1g of phosphorus trichloride and 20mL of anhydrous ether, heating and refluxing for 2 hours after dropwise adding, slowly cooling to room temperature, hydrolyzing by using an ammonium chloride aqueous solution, separating an organic phase by using a flow-dividing funnel, extracting a water layer by using ether, combining the organic phase and an extract, drying by using anhydrous magnesium sulfate, distilling off the ether under reduced pressure, distilling under reduced pressure by using an oil pump, collecting a fraction of 160-class organic solvent, and obtaining the phosphorus ligand at 200 ℃.
The intermediate (163mg) and phosphine ligand (98mg) were combined in benzene (10mL) under nitrogen and stirred at room temperature for 5 min. The solvent was removed in vacuo and the resulting brown residue was washed with 4X 20mL of pentane and dried in vacuo. The compound was obtained as a brown powder.
The product has the following spectrogram analysis data:
the molecular formula is as follows: c55H65N2O3PCl2Ru
m/z：1004.67(100％)
Elemental Analysis：C:65.78；H:6.60；P:3.13
HNMR(400MHz)：
δ＝7.52-7.44(5H,m)；4.15-4.76(39H,m)；2.23-2.75(21H,m)。
Example 3
The 3# ruthenium carbene catalyst and the synthesis method thereof comprise the following steps:
under nitrogen, the dibasic Grubbs catalyst (4.0g) was dissolved in toluene (10mL) and 2, 6-lutidine (34mL) was added. The reaction was stirred at room temperature for 15 minutes during which time a color change from red to bright green was observed. The reaction mixture was transferred through a cannula into 100mL of cold (-10 ℃) pentane and a green solid precipitated. The precipitate was filtered, washed with 4X 50mL pentane and dried under vacuum to give a green powder of pyridine-containing intermediate.
Under the protection of nitrogen, a constant-pressure dropping funnel and a reflux condenser tube are quickly arranged on a dried 250m L three-necked bottle, 5.3g of crushed magnesium chips are added into the three-necked bottle, 50mL of anhydrous ether is added for covering, 3.8mL of 1-bromine-4-isopropoxybenzene is added dropwise, and one piece of iodine is added for heating and refluxing. When the color of iodine fades to become grey turbid liquid, 36.2g of 1-bromo-4-isopropoxybenzene and 100mL of anhydrous ether are prepared into a mixed solution, the mixed solution is placed in a constant-pressure dropping funnel, a small amount of the mixed solution is slowly dropped into a reaction bottle, heat is released for reflux, and after the dropping is finished, the mixed solution is heated for reflux for 2 hours. And (2) placing the reaction bottle at-78 ℃, slowly dropwise adding a mixed solution of 7.3g of phosphorus trichloride and 20mL of anhydrous ether, heating and refluxing for 2 hours after dropwise adding, slowly cooling to room temperature, hydrolyzing by using an ammonium chloride aqueous solution, separating an organic phase by using a flow-dividing funnel, extracting a water layer by using ether, combining the organic phase and an extract, drying by using anhydrous magnesium sulfate, distilling off the ether under reduced pressure, distilling under reduced pressure by using an oil pump, collecting a fraction of 160-class organic solvent, and obtaining the phosphorus ligand at 200 ℃.
The intermediate (167mg) and phosphine ligand (102mg) were combined in benzene (10mL) under nitrogen and stirred at room temperature for 20 min. The solvent was removed in vacuo and the resulting brown residue was washed with 4X 20mL of pentane and dried in vacuo. The compound was obtained as a brown powder.
Spectral analysis data of the product:
the molecular formula is as follows: c55H65N2O3PCl2Ru
m/z：1004.67(100％)
Elemental Analysis：C:65.86；H:6.50；P:3.14
HNMR(400MHz)：
δ＝7.52-7.44(5H,m)；4.15-4.76(39H,m)；2.23-2.75(21H,m)。
Application examples 1 to 6
Application of 1# ruthenium carbene catalyst in catalytic preparation of dicyclopentadiene
The amount ratio of dicyclopentadiene to 1# ruthenium carbene catalyst material in the following application examples is 5000:1, 10000:1, 15000:1, 20000:1, 30000:1, 50000:1 respectively. The tensile (GB/T2567-2008), bending properties (GB/T2567-2008), impact strength (GB/T2567-2008), elongation at break (GB/T2567-2008) and heat distortion temperature properties (ISO 75-1987) of the dicyclopentadiene homopolymer obtained are shown in Table 1.
The following description of the specific catalytic reaction is given by taking dicyclopentadiene and No. 1 ruthenium carbene catalyst in a mass ratio of 5000:1 (about 800: 1):
(1) preparing a catalyst solution A
The ruthenium carbene catalyst prepared in example 1 (424.5mg, 0.5mmol) was weighed in a glove box and dissolved in 10.6ml of dichloromethane to prepare a 40mg/ml catalyst solution.
(2) Preparing dicyclopentadiene solution B
Adding excessive calcium hydride into dicyclopentadiene (with the purity of more than 95 percent), stirring for 12 hours at the temperature of 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5 percent of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant (o-di-tert-butyl-p-methylphenol) with the mass of 0.01-2% of that of dicyclopentadiene into the dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring the mixture on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.
(3) Mixed solidification forming
Measuring 3.85ml of A solution and 120g of B solution, quickly mixing the A solution and the B solution under the protection of nitrogen, and mixing uniformly. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.
And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.
TABLE 1 mechanical Properties of the polymers at different proportions of monomer and catalyst
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A ruthenium carbene catalyst having the structural formula shown below:
2. the method of preparing a ruthenium carbene catalyst as recited in claim 1, comprising:
(1) dissolving and mixing the Grubbs second-generation catalyst (II) and a pyridine compound in an organic solvent, stirring for reaction, and carrying out post-treatment to obtain a green ruthenium carbene catalyst (III) containing pyridine;
wherein the GrubbsII catalyst has a structure shown in a formula (II):
the structure of the ruthenium carbene catalyst containing pyridine is shown as the formula (III):
wherein R is H, CH3
(2) 1-bromine-4-isopropoxybenzene and crushed magnesium chips are placed in an organic solvent, after reflux reaction is carried out for 2 hours at room temperature, phosphorus trichloride is added into reaction liquid, heating and reflux are continuously carried out for 2 hours, and then the reaction liquid is extracted to obtain ligand tri (4-isopropoxybenzene) phosphine (IV);
wherein the ligand tri (4-isopropoxy benzene) phosphine has a structure shown in a formula (IV):
(3) dissolving the ruthenium carbene catalyst (III) containing pyridine prepared in the step (1) by using an organic solvent, adding the ligand tri (4-isopropoxy benzene) phosphine (IV) prepared in the step (2), stirring to react until the color of the solution is brown, and carrying out post-treatment to obtain the ruthenium carbene structural compound shown in the formula (I).
3. The method of claim 2, wherein: the mass ratio of the Grubbs secondary catalyst (II) to the pyridine compound in the step (1) is 1: 1-5.
4. The production method according to claim 2, characterized in that: the stirring reaction temperature in the step (1) is 10-40 ℃, and the reaction time is 10min-1 h.
5. The production method according to claim 2, characterized in that: the post-treatment in the step (1) comprises the following specific operations: transferring the stirred mixture into a low-temperature solvent through a sleeve, sequentially precipitating, filtering, washing and drying under vacuum to obtain a ruthenium carbene catalyst (III) containing pyridine; wherein the solvent is alkane, naphthenic hydrocarbon or aromatic hydrocarbon compound with the carbon atom number less than 20.
6. The production method according to claim 2, characterized in that: the molar ratio of the 1-bromo-4-isopropoxybenzene, the magnesium and the phosphorus trichloride in the step (2) is 1-10:1-10: 1.
7. The method of claim 2, wherein: in the step (2), 1-bromine-4-isopropoxybenzene and crushed magnesium chips are placed in an organic solvent, heated and refluxed for reaction for 2 hours, then slowly cooled to room temperature, phosphorus trichloride is slowly dripped into the reaction liquid at the ambient temperature of-100-0 ℃, then the heating and refluxing are continued for 2 hours, and the reaction liquid is extracted to obtain the ligand tri (4-isopropoxybenzene) phosphine (IV).
8. The production method according to claim 2, characterized in that: the molar ratio of the ruthenium carbene catalyst (III) containing pyridine to the ligand tri (4-isopropoxybenzene) phosphine (IV) in the step (3) is 1: 1-5.
9. The method of claim 2, wherein: the post-treatment in the step (3) comprises the following specific operations: removing the solvent from the stirred solution in vacuum, washing the obtained residue with the solvent, and drying in vacuum to obtain the ruthenium carbene structural compound shown in the formula (I); wherein the solvent is alkane, naphthenic hydrocarbon or aromatic hydrocarbon compound with the carbon atom number less than 20.
10. The method of claim 2, wherein: the stirring reaction temperature in the step (3) is 5-30 ℃, and the reaction time is 5min-1 h.
11. The method of claim 2, wherein: according to the preparation method, all the steps are carried out under the protection of nitrogen.
12. The use of the ruthenium carbene catalyst of claim 1 to catalyze olefin ring-opening metathesis reactions.
13. Use according to claim 12, characterized in that: the olefin ring-opening metathesis in the application method specifically comprises the following steps: dissolving the ruthenium carbene catalyst in an organic solvent to obtain a mixed solution A, dissolving dicyclopentadiene, a modifier and an antioxidant in the organic solvent to obtain a mixed solution B, fully and uniformly mixing the mixed solution A and the mixed solution B, immediately injecting the mixed solution A and the mixed solution B into a mold, carrying out ring-opening metathesis reaction on olefin at 40-80 ℃, curing and forming, and carrying out post-treatment at 120-150 ℃.
14. Use according to claim 12, characterized in that: the mass ratio of the dicyclopentadiene to the ruthenium carbene catalyst is 5000-50000: 1.
15. Use according to claim 12, characterized in that: the temperature of the olefin ring-opening metathesis reaction is 50-70 ℃, and the reaction time is 5-10 minutes.
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